Olefin polymer and method for producing same

Abstract

The present invention relates to an olefin-based polymer and a method for producing the same. The olefin-based polymer according to the embodiment of the present invention has a wide molecular weight distribution and excellent processability, and has excellent mechanical strength and heat sealability due to the relatively large amount of short chain branches in the high molecular weight component.

Description

[Technical field]

[0001] The present invention relates to an olefin-based polymer and a method for producing the same. Specifically, the present invention relates to an olefin-based polymer having excellent mechanical strength and a method for producing the same. [Background technology]

[0002] Metallocene catalysts, which are one of the catalysts used to polymerize olefins, are compounds in which ligands such as cyclopentadienyl, indenyl, and cycloheptadienyl are coordinated to a transition metal or a transition metal halide, and have a sandwich structure as their basic form.

[0003] In contrast to Ziegler-Natta catalysts, another catalyst used to polymerize olefins, in which the metal components that act as active sites are dispersed on the surface of an inert solid, and the properties of the active sites are not uniform, metallocene catalysts are known as single-site catalysts, as they are a single compound with a fixed structure and all active sites have the same polymerization characteristics. Polymers polymerized with such metallocene catalysts have narrow molecular weight distributions, uniform comonomer distributions, and higher copolymerization activity than Ziegler-Natta catalysts.

[0004] Meanwhile, linear low-density polyethylene (LLDPE) is produced by copolymerizing ethylene and alpha-olefins at low pressure using a polymerization catalyst, and has a narrow molecular weight distribution, short chain branches (SCB) of a certain length, and generally does not have long chain branches (LCB). Films made from linear low-density polyethylene have high breaking strength and elongation, excellent tear strength, impact strength, etc. in addition to the properties of general polyethylene, and are widely used in stretch films and overlap films where it is difficult to apply existing low-density polyethylene and high-density polyethylene.

[0005] However, linear low density polyethylene produced by metallocene catalysts has poor processability due to its narrow molecular weight distribution, and films produced therefrom tend to have poor heat sealability.

[0006] Therefore, there is a demand for olefin polymers which are excellent in processability and can be used to produce films having excellent mechanical strength and heat sealability. Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide an olefin polymer from which an olefin polymer film having excellent processability, mechanical strength and heat sealability can be produced.

[0008] Another object of the present invention is to provide a process for producing the above olefin polymer. [Means for solving the problem]

[0009] According to one embodiment of the present invention, (1) the density is 0.915 to 0.935 g / cm 3, preferably 0.918 to 0.932 g / cm 3 (2) Melt index (I 21.6 ) and the melt index (I 2.16 (3) an olefin polymer having a comonomer distribution slope (CDS) defined by the following mathematical formula 1 of 1.0 or more, preferably 1.0 to 3.0:

number

[0010] In an embodiment of the present invention, the olefin polymer may be prepared by polymerizing an olefin monomer in the presence of a hybrid catalyst including at least one first transition metal compound represented by the following formula 1 and at least one second transition metal compound represented by the following formula 2: [ka] In the above chemical formula, each n is independently an integer of 1 to 20, M is independently titanium (Ti), zirconium (Zr) or hafnium (Hf); X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 6-20 Aryl, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20Alkyl, C 1-20 Alkylamide or C 6-20 is an aryl amide, R1 to R8 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamides, substituted or unsubstituted C 6-20 Arylamide, substituted or unsubstituted C 1-20 Alkylidene, or substituted or unsubstituted C 1-20 Cyril, R9~R 11 and R 12 ~R 14 each independently represents a substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamides, substituted or unsubstituted C 6-20 Arylamide, substituted or unsubstituted C 1-20 Alkylidene, or substituted or unsubstituted C 1-20 Cyril, R1 to R8 each independently represent a substituted or unsubstituted saturated or unsaturated C 4-20 A ring may be formed.

[0011] In an embodiment of the present invention, M is zirconium or hafnium, and X is a halogen or C. 1-20 alkyl, and R1 to R8 are each hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Alkenyl, or substituted or unsubstituted C 6-20 Aryl, R to R 11 and R 12 ~R 14 are substituted or unsubstituted C 1-20 It can be alkyl.

[0012] In a preferred embodiment of the present invention, the first transition metal compound may be at least one of the transition metal compounds represented by the following chemical formulas 1-1 to 1-3, and the second transition metal compound may be a transition metal compound represented by the following chemical formula 2-1. [ka] In the above formula, Me is a methyl group.

[0013] In an embodiment of the present invention, the molar ratio of the secondary transition metal compound to the first transition metal compound ranges from 100:1 to 1:100.

[0014] In an embodiment of the present invention, the catalyst may include at least one promoter selected from the group consisting of a compound represented by the following formula 3, a compound represented by the following formula 4, and a compound represented by the following formula 5. [ka] [Chemical formula 5] [LH] + [Z(A)4] - or [L] + [Z(A)4] - In the above Chemical Formula 3, n is an integer of 2 or more, and R a is a halogen atom, C 1-20C substituted with hydrocarbon or halogen groups 1-20 is a hydrocarbon group, In the above formula 4, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, C 1-20 Hydrocarbon radicals, halogen-substituted C 1-20 Hydrocarbon group or C 1-20 is an alkoxy group, In the above formula 5, L is a neutral or cationic Lewis base, [LH] + and [L] + is a Bronsted acid, Z is a Group 13 element, and each A is independently a substituted or unsubstituted C 6-20 Aryl group or substituted or unsubstituted C 1-20 It is an alkyl group.

[0015] In an embodiment of the present invention, the catalyst may further comprise a support supporting the transition metal compound, the cocatalyst compound, or both.

[0016] In a preferred embodiment of the present invention, the support may comprise at least one selected from the group consisting of silica, alumina and magnesia.

[0017] Here, the total amount of the mixed transition metal compounds supported on the support is 0.001 to 1 mmole per 1 g of the support, and the total amount of the promoter compounds supported on the support is 2 to 15 mmole per 1 g of the support.

[0018] In a specific embodiment of the present invention, the olefin polymer is a copolymer of an olefin monomer and an olefin comonomer. Specifically, the olefin monomer may be ethylene, and the olefin comonomer may be at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, and 1-hexadecene. Preferably, the olefin polymer is a linear low-density polyethylene in which the olefin monomer is ethylene and the olefin comonomer is 1-hexene.

[0019] According to one embodiment of the present invention, the present invention provides a process for producing an olefin polymer by polymerizing an olefin monomer in the presence of a hybrid catalyst comprising at least one first transition metal compound represented by the above-mentioned chemical formula 1 and at least one second transition metal compound represented by the above-mentioned chemical formula 2, and the olefin polymer (1) has a density of 0.915 to 0.935 g / cm 3 , preferably 0.918 to 0.932 g / cm 3 (2) Melt index (I 21.6 ) and the melt index (I 2.16 (3) a melt flow ratio (MFR) of 15 or more, preferably 15 to 40; and (3) a comonomer distribution slope (CDS) defined by the above mathematical formula 1 of 1.0 or more, preferably 1.0 to 3.0.

[0020] In an embodiment of the present invention, the polymerization of the olefinic monomer may be carried out in a slurry polymerization, specifically, the polymerization of the olefinic monomer may be carried out in a slurry batch reactor. Effect of the Invention

[0021] The olefin polymer according to the embodiment of the present invention has a wide molecular weight distribution and excellent processability, and since the high molecular weight component contains a relatively large number of short chain branches, it has excellent mechanical strength and heat sealability. [Brief description of the drawings]

[0022] [Figure 1] 1 is a GPC-FTIR graph for explaining a method for measuring CDS defined by Equation 1. [Diagram 2] 1 is a GPC-FTIR graph for CDS measurement of the olefin polymer of Example 1. [Diagram 3] 1 is a GPC-FTIR graph for CDS measurement of the olefin polymer of Example 2. [Figure 4] 1 is a GPC-FTIR graph for CDS measurement of the olefin polymer of Example 3. [Diagram 5] 1 is a GPC-FTIR graph for CDS measurement of the olefin polymer of Example 4. [Figure 6] 1 is a GPC-FTIR graph for CDS measurement of the olefin polymer of Example 5. [Figure 7] 1 is a GPC-FTIR graph for CDS measurement of the olefin polymer of Example 6. [Figure 8] 1 is a GPC-FTIR graph for CDS measurement of the olefin polymer of Example 7. [Figure 9] 1 is a GPC-FTIR graph for CDS measurement of the olefin polymer of Example 8. [Figure 10] 1 is a GPC-FTIR graph for CDS measurement of the olefin polymer of Comparative Example 1. [Figure 11] 1 is a GPC-FTIR graph for CDS measurement of the olefin polymer of Comparative Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The present invention will now be described in more detail.

[0024] Olefin Polymers According to one embodiment of the present invention, (1) the density is 0.915 to 0.935 g / cm 3 (2) Melt index (I 21.6 ) and the melt index (I 2.16 (3) an olefin polymer having a comonomer distribution slope (CDS) defined by the following mathematical formula 1 of 1.0 or more.

[0025] In a specific example of the present invention, the olefin polymer has a density of 0.915 to 0.935 g / cm 3 Preferably, the density of the olefin polymer is 0.918 to 0.932 g / cm 3 It can be.

[0026] In an embodiment of the present invention, the olefin polymer has a melt index (I 21.6 ) and the melt index (I 2.16 ) is not less than 15. Preferably, the MFR of the olefin polymer is 15-40.

[0027] In a specific example of the present invention, the olefin-based polymer has a comonomer distribution slope (CDS) of 1.0 or more, as defined by the following mathematical formula 1. Preferably, the CDS of the olefin-based polymer may be 1.0 to 3.0.

[0028]

number

[0029] In the above mathematical formula 1, C 20 and C. 80are the comonomer contents at the cumulative weight fractions of 20% and 80%, respectively, in the comonomer distribution, and M 20 and M. 80 are the molecular weights at which the cumulative mass fractions are 20% and 80%, respectively, in the comonomer distribution.

[0030] The CDS of an olefin polymer indicates the gradient of the comonomer content against the molecular weight at the cumulative mass fractions of 20% and 80% on a comonomer distribution graph. The higher the CDS of an olefin polymer, the more the copolymer is concentrated in the polymer chain with a high molecular weight, resulting in excellent mechanical strength and heat sealability.

[0031] Here, the comonomer distribution of the olefin polymer can be continuously measured together with the molecular weight and molecular weight distribution of the polymer using a GPC-FTIR device.

[0032] The olefin polymer according to the embodiment of the present invention has a relatively broad molecular weight distribution and a relatively large amount of short chain branches in the high molecular weight component, and therefore, it is understood that the olefin polymer film produced therefrom has excellent mechanical strength and heat seal properties.

[0033] In an embodiment of the present invention, the olefin polymer may be prepared by polymerizing an olefin monomer in the presence of a hybrid catalyst including at least one first transition metal compound represented by the following formula 1 and at least one second transition metal compound represented by the following formula 2:

[0034] [ka]

[0035] In the above chemical formula, each n is independently an integer of 1 to 20, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5. Specifically, each n can be 1 or 2.

[0036] Each M is independently titanium (Ti), zirconium (Zr), or hafnium (Hf). Specifically, each M can be zirconium or hafnium.

[0037] X is independently halogen, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 6-20 Aryl, C 1-20 Alkyl C 6-20 Aryl, C 6-20 Aryl C 1-20 Alkyl, C 1-20 Alkylamide or C 6-20 Specifically, X is a halogen or C 1-20 Preferably, X is chlorine or methyl.

[0038] R1 to R8 are each independently hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamides, substituted or unsubstituted C 6-20 Arylamide, substituted or unsubstituted C 1-20 Alkylidene, or substituted or unsubstituted C 1-20 silyl, wherein R1 to R8 are each independently a substituted or unsubstituted saturated or unsaturated C 4-20 Specifically, R1 to R8 may each be hydrogen, a substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Alkenyl, or substituted or unsubstituted C6-20 It can be aryl.

[0039] R9~R 11 and R 12 ~R 14 each independently represents a substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 2-20 Alkenyl, substituted or unsubstituted C 6-20 Aryl, substituted or unsubstituted C 1-20 Alkyl C 6-20 Aryl, substituted or unsubstituted C 6-20 Aryl C 1-20 Alkyl, substituted or unsubstituted C 1-20 Heteroalkyl, substituted or unsubstituted C 3-20 Heteroaryl, substituted or unsubstituted C 1-20 Alkylamides, substituted or unsubstituted C 6-20 Arylamide, substituted or unsubstituted C 1-20 Alkylidene, or substituted or unsubstituted C 1-20 Specifically, R9 to R 11 and R 12 ~R 14 are substituted or unsubstituted C 1-20 Alkyl or substituted or unsubstituted C 6-20 Preferably, R to R 11 and R 12 ~R 14 can each be methyl.

[0040] In an embodiment of the present invention, M is zirconium or hafnium, and X is a halogen or C. 1-20 alkyl, and R1 to R8 are each hydrogen, substituted or unsubstituted C 1-20 Alkyl, substituted or unsubstituted C 1-20 Alkenyl, or substituted or unsubstituted C 6-20 Aryl, R to R 11 and R 12 ~R 14 are substituted or unsubstituted C 1-20 It can be alkyl.

[0041] In a preferred embodiment of the present invention, the first transition metal compound may be at least one of the transition metal compounds represented by the following chemical formulas 1-1 to 1-3, and the second transition metal compound may be a transition metal compound represented by the following chemical formula 2-1.

[0042] [ka]

[0043] In the above formula, Me is a methyl group.

[0044] In a specific example of the present invention, the molar ratio of the second transition metal compound to the first transition metal compound is in the range of 100:1 to 1:100. Preferably, the molar ratio of the second transition metal compound to the first transition metal compound is in the range of 50:1 to 1:50. Preferably, the molar ratio of the second transition metal compound to the first transition metal compound is in the range of 10:1 to 1:10.

[0045] In an embodiment of the present invention, the catalyst may include at least one promoter compound selected from the group consisting of a compound represented by the following formula 3, a compound represented by the following formula 4, and a compound represented by the following formula 5.

[0046] [ka]

[0047] In the above Chemical Formula 3, n is an integer of 2 or more, and R a is a halogen atom, C 1-20 Hydrocarbon or halogen substituted C 1-20 Specifically, R a can be methyl, ethyl, n-butyl or isobutyl.

[0048] [ka]

[0049] In the above formula 4, D is aluminum (Al) or boron (B), and R b , R c and R d are each independently a halogen atom, C 1-20 Hydrocarbon radicals, halogen-substituted C 1-20 Hydrocarbon group or C 1-20 Specifically, when D is aluminum (Al), R b , R c and R d can each independently be methyl or isobutyl, and when D is boron (B), R b , R c and R d can each be pentafluorophenyl.

[0050] [Chemical formula 5] [LH] + [Z(A)4] - or [L] + [Z(A)4] -

[0051] In the above formula 5, L is a neutral or cationic Lewis base, [LH] + and [L] + is a Bronsted acid, Z is a Group 13 element, and each A is independently a substituted or unsubstituted C 6-20 Aryl group or substituted or unsubstituted C 1-20 It is an alkyl group. Specifically, [LH] + can be a dimethylanilinium cation, [Z(A)4] - is [B(C6F5)4] - [L] + is [(C6H5)3C] + It can be.

[0052] Specifically, examples of the compound represented by Chemical Formula 3 include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, etc., and methylaluminoxane is preferred, but is not limited thereto.

[0053] Examples of the compound represented by Chemical Formula 4 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-p-tolylaluminum, dimethylaluminum methoxide, dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, and tributylboron. Of these, trimethylaluminum, triethylaluminum, and triisobutylaluminum are preferred, but the present invention is not limited thereto.

[0054] Examples of the compound represented by Chemical Formula 5 include triethylammonium tetraphenyl boron, tributylammonium tetraphenyl boron, trimethylammonium tetraphenyl boron, tripropylammonium tetraphenyl boron, trimethylammonium tetra(p-tolyl) boron, trimethylammonium tetra(o,p-dimethylphenyl) boron, tributylammonium tetra(p-trifluoromethylphenyl) boron, trimethylammonium tetra(p-trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenyl boron, N,N-diethylanilinium tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethylammonium tetrapentafluorophenyl boron, triphenylphosphonium tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethylammonium tetraphenyl aluminum, and tributylammonium tetraphenyl aluminum. ammonium, trimethylammonium tetraphenylaluminum, tripropylammonium tetraphenylaluminum, trimethylammonium tetra(p-tolyl)aluminum, tripropylammonium tetra(p-tolyl)aluminum, triethylammonium tetra(o,p-dimethylphenyl)aluminum, tributylammonium tetra(p-trifluoromethylphenyl)aluminum, trimethylammonium tetra(p-trifluoromethylphenyl)aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, diethylammonium tetrapentatetraphenylaluminum, triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra(p-tolyl)boron, triethylammonium tetra(o,p-dimethylphenyl) boron, tributylammonium tetra(p-trifluoromethylphenyl) boron, triphenylcarbonium tetra(p-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenyl boron, etc.

[0055] In an embodiment of the present invention, the catalyst may further comprise a support supporting the transition metal compound, the cocatalyst compound, or both. Specifically, the support may support both the transition metal compound and the cocatalyst compound.

[0056] Here, the support may include a material containing a hydroxyl group on the surface, and preferably, a material having a highly reactive hydroxyl group and a siloxane group that has been dried to remove moisture from the surface may be used. For example, the support may include at least one selected from the group consisting of silica, alumina, and magnesia. Specifically, silica, silica-alumina, and silica-magnesia that have been dried at high temperatures may be used as the support, and these may generally include oxides, carbonates, sulfates, and nitrates such as Na2O, K2CO3, BaSO4, and Mg(NO3)2. These may also include carbon, zeolite, magnesium chloride, and the like. However, the support is not limited to these, and is not particularly limited as long as it can support a transition metal compound and a promoter compound.

[0057] The carrier may have an average particle size of 10 to 250 μm, preferably an average particle size of 10 to 150 μm, and more preferably an average particle size of 20 to 100 μm.

[0058] The volume of the micropores in the support may be 0.1 to 10 cc / g, preferably 0.5 to 5 cc / g, and more preferably 1.0 to 3.0 cc / g.

[0059] The specific surface area of ​​the support is 1 to 1,000 m 2 / g, preferably 100 to 800 m 2 / g, more preferably 200 to 600 m 2 / g.

[0060] In a preferred embodiment of the present invention, the support may be silica. Here, the drying temperature for silica may be 200 to 900° C. The drying temperature may be preferably 300 to 800° C., more preferably 400 to 700° C. If the drying temperature is less than 200° C., there may be too much moisture on the surface, causing a reaction between the moisture and the promoter compound, and if the drying temperature exceeds 900° C., the structure of the support may collapse.

[0061] The concentration of hydroxyl groups in the dried silica may be 0.1 to 5 mmole / g, preferably 0.7 to 4 mmole / g, and more preferably 1.0 to 2 mmole / g. If the concentration of hydroxyl groups is less than 0.1 mmole / g, the amount of the first promoter compound supported will be low, and if it exceeds 5 mmole / g, a problem of inactivation of the catalyst component may occur.

[0062] The total amount of the transition metal compound supported on the carrier can be 0.001 to 1 mmole per 1 g of carrier. When the ratio of the transition metal compound to the carrier satisfies the above range, appropriate supported catalytic activity is exhibited, which is advantageous in terms of maintaining the activity of the catalyst and in terms of economic efficiency.

[0063] The total amount of the promoter compounds supported on the carrier may be 2 to 15 mmole per gram of carrier. If the ratio of the promoter compounds to the carrier satisfies the above range, it is advantageous in terms of maintaining the activity of the catalyst and economic efficiency.

[0064] One or more types of carriers may be used. For example, both the transition metal compound and the co-catalyst compound may be supported on one carrier, or the transition metal compound and the co-catalyst compound may be supported on two or more carriers. Also, only one of the transition metal compound and the co-catalyst compound may be supported on the carrier.

[0065] As a method for supporting a transition metal compound and / or a cocatalyst compound usable in an olefin polymerization catalyst, a physical adsorption method or a chemical adsorption method can be used.

[0066] For example, the physical adsorption method may be a method in which a solution in which a transition metal compound is dissolved is brought into contact with a support and then dried; a method in which a solution in which a transition metal compound and a promoter compound are dissolved is brought into contact with a support and then dried; or a method in which a solution in which a transition metal compound is dissolved is brought into contact with a support and then dried to produce a support on which the transition metal compound is supported, and separately, a solution in which a promoter compound is dissolved is brought into contact with a support and then dried to produce a support on which the promoter compound is supported, and then these are mixed together.

[0067] The chemical adsorption method may be a method in which a promoter compound is first supported on the surface of a support, and then a transition metal compound is supported on the promoter compound, or a method in which a catalyst compound is covalently bonded to a functional group on the surface of the support (e.g., in the case of silica, a hydroxyl group (-OH) on the surface of the silica).

[0068] In an embodiment of the present invention, the olefin polymer may be a homopolymer of an olefin monomer or a copolymer of an olefin monomer and a comonomer. Preferably, the olefin polymer is a copolymer of an olefin monomer and an olefin comonomer.

[0069] Here, the olefin monomer is C 2-20 Alpha-olefin, C 1-20 Diolefin, C 3-20 Cycloolefin and C 3-20 At least one selected from the group consisting of cyclodiolefins.

[0070] For example, the olefin monomer may be ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, or 1-hexadecene, and the olefin polymer may be a homopolymer containing only one of the olefin monomers exemplified above, or a copolymer containing two or more of them.

[0071] In an exemplary embodiment, the olefin polymer comprises ethylene and C 3-20 The olefin polymer may be a copolymer in which an alpha-olefin is copolymerized. Preferably, the olefin polymer may be a linear low-density polyethylene in which the olefin monomer is ethylene and the olefin comonomer is 1-hexene.

[0072] In this case, the content of ethylene is preferably 55 to 99.9% by weight, more preferably 90 to 99.9% by weight, and the content of the alpha-olefin comonomer is preferably 0.1 to 45% by weight, more preferably 0.1 to 10% by weight.

[0073] Method for producing olefin polymer According to one embodiment of the present invention, there is provided a method for producing an olefin polymer, comprising the step of polymerizing an olefin monomer in the presence of a hybrid catalyst comprising at least one first transition metal compound represented by the following chemical formula 1 and at least one second transition metal compound represented by the following chemical formula 2 to obtain an olefin polymer:

[0074] [ka]

[0075] In the above chemical formula, n, M, X, R1 to R8 and R9 to R 14 is as explained in the section on olefin polymers above.

[0076] As described above, the olefin polymer produced by the production method according to one embodiment of the present invention has the following characteristics: (1) a density of 0.915 to 0.935 g / cm 3 , preferably 0.918 to 0.932 g / cm 3 (2) Melt index (I 21.6 ) and the melt index (I 2.16 (3) the comonomer distribution slope (CDS) defined by the following mathematical formula 1 can be 1.0 or more, preferably 1.0 to 3.0.

[0077]

number

[0078] C in the above mathematical formula 1 20 , C 80 , M 20 and M. 80 is as explained in the section on olefin polymers above.

[0079] In an embodiment of the present invention, the olefin polymer may be polymerized by a polymerization reaction such as, but not limited to, free radical, cationic, coordination, condensation, and addition.

[0080] As an embodiment of the present invention, the olefin polymer may be produced by a gas phase polymerization method, a solution polymerization method, a slurry polymerization method, etc. Preferably, the polymerization of the olefin monomer may be performed by slurry polymerization, and more specifically, the polymerization of the olefin monomer may be performed in a slurry batch reactor.

[0081] When olefin polymers are produced by solution polymerization or slurry polymerization, examples of usable solvents include C tetrahydrofurans such as pentane, hexane, heptane, nonane, decane, and their isomers. 5-12 Examples of the solvent include, but are not limited to, aliphatic hydrocarbon solvents; aromatic hydrocarbon solvents such as toluene and benzene; chlorine-substituted hydrocarbon solvents such as dichloromethane and chlorobenzene; and mixtures thereof.

[0082] Working Example The present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited to these examples.

[0083] Manufacturing Example The transition metal compound of formula 1-1 (bis[(1-butyl-3-methyl)cyclopentadienyl]zirconium dichloride) and the transition metal compound of formula 1-2 (bis(n-butylcyclopentadienyl)zirconium dichloride) were purchased from TCI, and the transition metal compound of formula 2-1 was prepared as follows.

[0084] Preparation of 2-(trimethylsilylmethyl)-2-propen-1-ol A solution of 2-(trimethylsilylmethyl)allyl acetate (2.69g, 14.4mmole) in methanol (22ml) was slowly poured into an aqueous solution of potassium carbonate (K2CO3) (6.6M, 14.4mmole). After the addition was completed, the solution was stirred at room temperature for 4 hours. After stirring, water was added to terminate the reaction. The organic layer was extracted using diethyl ether, and the remaining water was removed using magnesium sulfate (MgSO4). All the solvent was removed under vacuum, yielding 1.51g (72%) of a pale beige oil compound.

[0085] 1 H-NMR (CDCl3, 300 MHz): δ 4.90-4.88 (m, 1H), 4.66 (s, 1H), 3.97 (s, 2H), 1.53 (s, 2H), 0.03 (s, 9H).

[0086] Preparation of 2-(trimethylsilylmethyl)methanesulfonate Methanesulfonyl chloride (1.8g, 15.7mmole) was slowly added to a solution of 2-(trimethylsilylmethyl)-2-propen-1-ol (1.51g, 10.5mmole) and triethylamine (1.91g, 18.8mmole) diluted in dichloromethane (30ml) at 0°C. The mixture was then stirred at 0°C for 3 hours. The reaction was terminated by adding aqueous sodium bicarbonate (NaHCO3) at 0°C, and the organic layer was separated by extraction with dichloromethane. The remaining water was removed with sodium sulfate (Na2SO4), and all the solvent was removed under vacuum to obtain 1.9g (82%) of a yellow oil compound.

[0087] 1 H-NMR (CDCl3, 300 MHz): δ5.03 (d, 1H), 4.84 (s, 1H), 4.56 (s, 2H), 3.02 (s, 3H), 1.60 (s, 2H), 0.06 (s, 9H).

[0088] Preparation of 2-(trimethylsilylmethyl)allyl bromide A solution of 2-(trimethylsilylmethyl)methanesulfonate (1.9g, 8.54mmole) diluted in tetrahydrofuran (THF) (20ml) was slowly added with a solution of lithium bromide dispersed in tetrahydrofuran (15ml) at room temperature, and the mixture was stirred at 110°C for 4 hours. Distilled water was added at 0°C to terminate the reaction, and the organic layer was separated by extraction with diethyl ether. The remaining water was removed with sodium sulfate, and then all the solvent was removed under vacuum to obtain 1.12g (65%) of a yellow oil compound.

[0089] 1 H-NMR (CDCl3, 300 MHz): δ5.04 (s, 1H), 4.74 (d, 1H), 3.90 (d, 2H), 1.72 (d, 2H), 0.05 (s, 9H).

[0090] Production of [2-(cyclopentadienylmethyl)allyl]trimethylsilane Sodium cyclopentadienide (3.04g, 6.49mmole, 2M THF solution) was slowly added dropwise to a solution of 2-(trimethylsilylmethyl)allyl bromide (1.12g, 5.41mmole) diluted in tetrahydrofuran (20ml) at -30℃, and the temperature was gradually raised to room temperature and stirred for 12 hours. Distilled water was added at 0℃ to terminate the reaction, and the organic layer was separated by extraction with diethyl ether. The remaining water was removed with magnesium sulfate, and then separated by column chromatography (hexane) to obtain 620mg (60%) of a pale beige oil compound.

[0091] 1 H-NMR (CDCl3, 300 MHz): δ6.42-6.02 (m, 4H), 4.60-4.55 (m, 2H), 3.06-2.97 (m, 2H), 2.87-2.85 (m, 2H), 1.54 (s, 2H), 0.03 (d, 9H).

[0092] Preparation of [2-(trimethylsilylmethyl)allyl]cyclopentadienyl lithium To a solution of [2-(cyclopentadienylmethyl)allyl]trimethylsilane (620 mg, 3.22 mmole) diluted in tetrahydrofuran (10 ml), n-butyllithium (n-BuLi) (1.44 g, 2.93 mmole, 1.6 M hexane solution) was slowly added at -30°C, and the temperature was gradually raised to room temperature and stirred for 12 hours. The solvent of the reaction solution was dried under vacuum, and then hexane was added and stirred for 15 minutes. The resulting solid was filtered and dried under vacuum to obtain 528 mg (83%) of a pale yellow solid compound.

[0093] Preparation of bis[(2-trimethylsilylmethylallyl)cyclopentadienyl]hafnium dichloride A solution of hafnium chloride (HfCl4) (226 mg, 0.71 mmole) dispersed in toluene (2 ml) was slowly added to a solution of [2-(trimethylsilylmethyl)allyl]cyclopentadienyllithium (280 mg, 1.41 mmole) diluted in toluene (3 ml) at -30°C, and the temperature was gradually raised to room temperature and stirred for 12 hours. When the reaction was completed, the reaction solution was filtered and the solvent of the filtrate was dried under vacuum. The resulting solid was washed with hexane and dried to obtain 180 mg (41%) of a white solid compound.

[0094] 1 H-NMR (CDCl3, 300 MHz): δ6.21 (t, 2H), 6.12 (t, 2H), 4.54 (d, 2H), 4.44 (d, 1H), 3.28 (s, 2H), 1.52 (s, 2H), 0.05 (s, 9H).

[0095] Preparation of bis[(2-trimethylsilylmethylallyl)cyclopentadienyl]hafniumdimethyl Bis[(2-trimethylsilylmethylallyl)cyclopentadienyl]hafnium dichloride (2.4g, 3.79mmole) was diluted in toluene (40ml) and MeMgBr (3.93g, 11.4mmole, 3.0M diethyl ether solution) was added slowly at -30℃, then the temperature was gradually raised to room temperature and stirred for 12 hours. After the reaction was completed, the mixture was extracted with toluene and filtered. After removing the toluene under vacuum, the mixture was washed with hexane and dried to obtain 2.08g (93%) of a white solid compound.

[0096] Manufacturing Example 1 17.9 mg of the transition metal compound of formula 1-1 and 57.0 mg of the transition metal compound of formula 2-1 were added to 8.71 g of a 10% toluene solution of methylaluminoxane and stirred at room temperature for 1 hour. After the reaction was completed, the solution was added to 1.94 g of silica (XPO-2402), and 15 ml of toluene was added and stirred at 70°C for 2 hours. The catalyst after the loading was completed was washed three times with 5 ml of toluene and dried overnight in a vacuum at 60°C to obtain 2.80 g of a powdered supported catalyst.

[0097] Manufacturing Example 2 2.6 g of a supported catalyst was obtained in the same manner as in Preparation Example 1, except that 15.5 mg of the transition metal compound of formula 1-2 was used instead of the transition metal compound of formula 1-1.

[0098] Examples 1 to 8 Using a slurry batch polymerization reactor, ethylene / 1-hexene copolymers were produced in the presence of the supported catalysts obtained in Preparation Examples 1 and 2. The polymerization conditions for the above examples are summarized in Table 1 below.

[0099] [Table 1]

[0100] Comparative Examples 1-2 For comparison, Hanwha Solutions' linear low-density polyethylene M1810HN (density 0.9180 g / cm 3 , melt index 1.0 g / 10 min; Comparative Example 1) and M2010EN (density 0.9200 g / cm 3 , melt index 1.0 g / 10 min; Comparative Example 2) was used.

[0101] Test Example The physical properties of the olefin polymers of the above examples were measured according to the following methods and standards, and the results are shown in Tables 2 and 3 below.

[0102] (1)density Measured according to ASTM D1505.

[0103] (2) Melt index and melt flow ratio (MFR) According to ASTM D 1238, the melt index was measured at 190°C under a load of 21.6 kg and 2.16 kg, and the ratio (MI 21.6 / MI 2.16 ) was sought.

[0104] (3) Comonomer Distribution Gradient (CDS) The measurements were performed at 170°C using gel permeation chromatography-FTIR (GPC-FTIR).

[0105] [Table 2]

[0106] [Table 3] [Industrial Applicability]

[0107] The olefin polymer according to the embodiment of the present invention has a wide molecular weight distribution and excellent processability, and since the high molecular weight component contains a relatively large number of short chain branches, it has excellent mechanical strength and heat sealability.

Claims

1. A hybrid catalyst for producing an olefin polymer, comprising at least one first transition metal compound represented by the following chemical formula 1 and at least one second transition metal compound represented by the following chemical formula 2: The olefin polymer has (1) a density of 0.915 to 0.935 g / cm ３ (2) Melt index (I) measured at 190° C. under a load of 21.6 kg ２１．６ ) and the melt index (I ２．１６ (3) a comonomer distribution slope (CDS) defined by the following Equation 1 is 1.0 or more. 【Chemistry 1】 In the above chemical formula, each n is independently an integer from 1 to 20, Each M is independently titanium (Ti), zirconium (Zr), or hafnium (Hf); X is independently halogen, C １－２０ Alkyl, C ２－２０ Alkenyl, C ２－２０ Alkynyl, C ６－２０ Aryl, C １－２０ Alkyl C ６－２０ Aryl, C ６－２０ Aryl C １－２０ Alkyl, C １－２０ Alkylamide or C ６－２０ is an aryl amide, R １ ~R ８ are each independently hydrogen, substituted or unsubstituted C １－２０ Alkyl, substituted or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted or unsubstituted C １－２０ Alkyl C ６－２０ Aryl, substituted or unsubstituted C ６－２０ Aryl C １－２０ Alkyl, substituted or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, substituted or unsubstituted C ６－２０ Arylamide, substituted or unsubstituted C １－２０ Alkylidene, or substituted or unsubstituted C １－２０ Cyril, R ９ ~R １１ and R １２ ~R １４ each independently represents a substituted or unsubstituted C １－２０ Alkyl, substituted or unsubstituted C ２－２０ Alkenyl, substituted or unsubstituted C ６－２０ Aryl, substituted or unsubstituted C １－２０ Alkyl C ６－２０ Aryl, substituted or unsubstituted C ６－２０ Aryl C １－２０ Alkyl, substituted or unsubstituted C １－２０ Heteroalkyl, substituted or unsubstituted C ３－２０ Heteroaryl, substituted or unsubstituted C １－２０ Alkylamide, substituted or unsubstituted C ６－２０ Arylamide, substituted or unsubstituted C １－２０ Alkylidene, or substituted or unsubstituted C １－２０ Cyril, R １ ~R ８ each independently represents a substituted or unsubstituted saturated or unsaturated C ４－２０ A ring may be formed. [Mathematical formula 1] CDS=(C ８０ -C ２０ ) / (logM ８０ -logM ２０ ) Here, C ２０ and C. ８０ are the comonomer contents at the cumulative weight fractions of 20% and 80%, respectively, in the comonomer distribution; M ２０ and M. ８０ are the molecular weights of the comonomer distribution at which the cumulative mass fractions are 20% and 80%, respectively.

2. M is zirconium or hafnium, and X is a halogen or C. １－２０ alkyl, R １ ~R ８ are each hydrogen, substituted or unsubstituted C １－２０ Alkyl, substituted or unsubstituted C １－２０ Alkenyl, or substituted or unsubstituted C ６－２０ aryl, R ９ ~R １１ and R １２ ~R １４ each represents a substituted or unsubstituted C １－２０ 2. The hybrid catalyst for producing an olefin polymer according to claim 1, wherein the olefin is an alkyl group.

3. The hybrid catalyst for producing an olefin polymer according to claim 1, wherein the first transition metal compound is at least one of the transition metal compounds represented by the following chemical formulas 1-1 to 1-3, and the second transition metal compound is a transition metal compound represented by the following chemical formula 2-1. 【Chemistry 2】 In the above chemical formula, Me is a methyl group.

4. 2. The hybrid catalyst for producing olefin polymers according to claim 1, wherein the molar ratio of the secondary transition metal compound to the primary transition metal compound is in the range of 100:1 to 1:

100.

5. The hybrid catalyst for producing an olefin polymer according to claim 1, wherein the catalyst comprises at least one cocatalyst compound selected from the group consisting of a compound represented by the following formula 3, a compound represented by the following formula 4, and a compound represented by the following formula 5. 【Chemistry 3】 [Chemical formula 5] [L-H] ＋ [Z(A) ４ ] － Or [L] ＋ [Z(A) ４ ] － In the above formula 3, n is an integer of 2 or more, R ａ is a halogen atom, C １－２０ C substituted with a hydrocarbon group or halogen １－２０ is a hydrocarbon group, In the above formula 4, D is aluminum (Al) or boron (B), R ｂ , R ｃ and R ｄ are each independently a halogen atom, C １－２０ Hydrocarbon groups, halogen-substituted C １－２０ Hydrocarbon group or C １－２０ is an alkoxy group, In the above formula 5, L is a neutral or cationic Lewis base, [L-H] ＋ and [L] ＋ is a Bronsted acid, Z is a Group 13 element, and each A is independently a substituted or unsubstituted C ６－２０ an aryl group or a substituted or unsubstituted C １－２０ It is an alkyl group.

6. 6. The hybrid catalyst for producing olefin polymers according to claim 5, wherein the catalyst further comprises a support supporting the transition metal compound, the cocatalyst compound or both.

7. 7. The hybrid catalyst for producing an olefin polymer according to claim 6, wherein the support comprises at least one selected from the group consisting of silica, alumina and magnesia.

8. The hybrid catalyst for producing an olefin polymer according to claim 6, wherein the total amount of the hybrid transition metal compounds supported on the support is 0.001 to 1 mmole per 1 g of the support, and the total amount of the co-catalyst compounds supported on the support is 2 to 15 mmole per 1 g of the support.

9. 2. The hybrid catalyst for producing an olefin polymer according to claim 1, wherein the olefin polymer is a copolymer of an olefin monomer and an olefin comonomer.

10. The hybrid catalyst for producing an olefin polymer according to claim 9, wherein the olefin monomer is ethylene, and the olefin comonomer is at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, and 1-hexadecene.

11. 11. The hybrid catalyst for producing an olefin polymer according to claim 10, wherein the olefin polymer is a linear low-density polyethylene in which the olefin monomer is ethylene and the olefin comonomer is 1-hexene.

12. The present invention relates to a method for producing an olefin polymer comprising the steps of: (1) polymerizing an olefin monomer in the presence of a hybrid catalyst comprising at least one first transition metal compound represented by the following chemical formula 1; and at least one second transition metal compound represented by the following chemical formula 2 to obtain an olefin polymer; and (2) obtaining an olefin polymer having a density of 0.915 to 0.935 g / cm3. ３ (2) Melt index (I) measured at 190° C. under a load of 21.6 kg ２１．６ ) and the melt index (I ２．１６ (3) a comonomer distribution slope (CDS) defined by the following mathematical formula 1 is 1.0 or more. 【Chemistry 4】 In the above chemical formula, each n is independently an integer from 1 to 20, Each M is independently titanium (Ti), zirconium (Zr), or hafnium (Hf); X's are each independently halogen, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 6-20 aryl, C 1-20 alkyl C 6-20 aryl, C 6-20 aryl C 1-20 alkyl, C 1-20 alkylamido or C 6-20 arylamido; R 1 to R 8 are each independently hydrogen, substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 alkylC 6-20 aryl, substituted or unsubstituted C 6-20 arylC 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkylamido, substituted or unsubstituted C 6-20 arylamido, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl; R 9 to R 11 and R 12 to R 14 are each independently substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted C 2-20 alkenyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted C 1-20 alkylC 6-20 aryl, substituted or unsubstituted C 6-20 arylC 1-20 alkyl, substituted or unsubstituted C 1-20 heteroalkyl, substituted or unsubstituted C 3-20 heteroaryl, substituted or unsubstituted C 1-20 alkylamido, substituted or unsubstituted C 6-20 arylamido, substituted or unsubstituted C 1-20 alkylidene, or substituted or unsubstituted C 1-20 silyl; Adjacent groups of R 1 to R 8 may each independently be linked to form a substituted or unsubstituted saturated or unsaturated C 4-20 ring. [Mathematical formula 1] CDS=(C ８０ -C ２０ ) / (logM ８０ -logM ２０ ) Here, C20 and C80 are the comonomer contents at the points where the cumulative weight fraction in the comonomer distribution is 20% and 80%, respectively, and M20 and M80 are the molecular weights at the points where the cumulative weight fraction in the comonomer distribution is 20% and 80%, respectively.

13. The method for producing an olefin polymer according to claim 12, wherein the polymerization of the olefin monomer is carried out by slurry polymerization.

14. The olefin polymer has a density of 0.918 to 0.932 g / cm ３ (2) the MFR is 15 to 40; and the CDS is 1.0 to 3.0.

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